Indoline dyestuffs

ABSTRACT

Indoline dyestuffs of the formula   WHEREIN R1 and R2 independently of one another denote alkyl, cycloalkyl or aralkyl or conjointly form a cycloalkyl ring, R3 denotes hydrogen, alkyl, cycloalkyl, aryl or aralkyl, R4 denotes hydrogen, alkyl, nitrile, carbamoyl, N-alkylcarbamoyl, alkoxycarbonyl or aralakoxycarbonyl, A represents the remaining members of a dibenzofurane radical which is optionally substituted further, and X represents a nitrile, carboxylic acid ester or carboxylic acid amide group are suitable for dyeing and printing synthetic fibre materials.

[ Mar. 25, 1975 1 IN DOLINE DYESTUFFS [75] Inventor: Hans-PeterKiihlthau,Leverkusen,

Germany [73] Assignee: Bayer Aktiengesellschaft, Leverkusen, Germany[22] Filed: Mar. 9, 1973 [21] Appl. No.: 339,828

[30] Foreign Application Priority Data Mar. 11, 1972 Germany .l 221195952 us. Cl 260/240 J, 8/54.2, 8/62, 8/63, 8/178 E, 8/178 R, 8/179,260/316.1l R, 260/3462 M [51] lnt. Cl. C07d 27/36, C09b 23/00 58 Fieldof Search 260/326.11 R, 2405 [561 References Cited UNITED STATES PATENTS3.468.619 9/1969 Raue et a1 8/25 OTHER PU BLlCATlONS Coenen et a1.,Zeitschrift fur Elektochemie, Vol. 57, pages 785 to 795 (1953).

The Ring Index, Supplement 11, page 317 and frontispage (1964).

Primary Examiner.lohn D. Randolph Attorney, Agent, or Firm-Plumley &Tyner [57] ABSTRACT lndoline dyestuffs oi the formula R R; A ON /LNJ=CCH=C/ l I h \X ,Rs

, wherein R, and R independently of one another de- 10 Claims, N0Drawings INDOLINE DYESTUFFS The subject ofthe present invention areindoline dyestuffs of the formula in which R and R independently of oneanother denote alkyl,

cycloalkyl or aralkyl or conjointly form a cycloalkyl ring, R denoteshydrogen, alkyl, cycloalkyl, aryl or aralkyl, R denotes hydrogen, alkyl,nitrile, carbamoyl, N-

alkylcarbamoyl, alkoxycarbonyl or aralkoxycarbonyl,

A represents the remaining members of a dibenzofurane radical which isoptionally substituted further, and X represents a nitrile, carboxylicacid ester or carboxylic acid amide group,

as well as processes for their manufacture and their use.

Suitable alkyl radicals R and R are, in particular, methyl and ethylradicals.

A suitable isolated cycloalkyl radical'R and R is the cyclohexylradical.

Suitable cycloalkyl radicals which can be formed by R and R conjointlyare cyclohexyl and cyclopentyl radicals.

Suitable aralkyl radicals R R and R are phenylalkyl radicals whichpreferably have 1 to 4 C atoms in the alkyl group and are optionallysubstituted in the phenyl radical by halogen, C -C alkyl or C -C alkoxy;as examples there may be mentioned benzyl, pchlorobenzyl, phenylethyl orphenylpropyl-(2,2).

Suitable aryl radicals R are naphthyl and above all phenyl radicalswhich can be substituted by, for example. halogen, Cl-C -alkyl or C1-C-alkoxy; as examples there may be mentioned: 4-tolyl, Z-chlorophenyl, 4-bromophenyl, 2-methyl-4-fluorophenyl and others.

Suitable alkyl radicals R and R are saturated or unsaturated alkylgroups with 1 6 atoms which can optionally be substituted further, forexample by hydroxyl. halogen. nitrile, C -C -alkoxy, CONH C -Calkoxycarbonyl or C -C -alkylcarbonyloxy.

As examples there may be mentioned: methyl, ethyl, chloroethyl andbromoethyl, hydroxyethyl, cyanoethyl, methoxypropyl, acetoxyethyl,allyl, nand i-propyl and n-. ior t-hutyl.

Suitable alkoxycarbonyl groups and N- alkylcarbamoyl groups R, are thosewith l 4 C atoms in the alkyl or alkoxy radical.

Suitable aralkoxycarbonyl groups phenyl-(C -C )-alkoxycarbonyl groups.

The dibenzofurane radical A can also be substituted, for example bychlorine. bromine, fluorine, C C,- alkyl. benzyl, C,-C -alkoxy, nitro,hydroxyl, nitrile, CF C,-C -all ylcarbonyl, C -C -alkoxycarbonyl,carbamoyl, N-C -C -alkoxycarbamoyl, C -C alkylcarbonylamino,benzoylamino, toloylamino, sulphamoyl, NC,-C,-alkylsulphamoyl, N,N-C-C,,-dialkylsulphamoyl, N,N-C -C -dialkylsulphamoyl, C -Calkylsulphonyl, phenylsulphonyl, tolyl- R, are

sulphonyl, phenoxy, tolyloxy and benzyloxy. In addition, the benzenering of the dibenzofurane radical A which is not bonded to the pyrrolering can possess a fused benzene ring.

By carboxylic acid ester groups X there are to be understood radicalswhich correspond to the formula -CO Q, wherein Q denotes alkyl,cycloalkyl, aralkyl or-hetoryalkyl.

By carboxylic acid amide groups X there are to be understood radicalswhich correspond to the formula CONV V wherein V and V representhydrogen, alkyl, cycloalkyl or aralkyl as well as those wherein V and Vconjointly with a N-atom form a heterocy- *clic structure.

Suitable alkyl radicals Q, V and V are above all saturated andunsaturated alkyl radicals with l 6 C atoms which can carry furthersubstituents such as, for example. hydroxyl, C,-C,-alkoxy. phenoxy ornitrile.

Suitable cycloalk'yl radicals, O, V, and V- are those with 5 7 C atoms,such as cyclohexyl, methylcyclohexyl and cyclopentyl.

Suitable aralkyl radicals 0, V and V: are phenylalkyl and phenylalkenylradicals which can be substituted in the benzene ring, for example by N0Cl, F, Br. OCH or CH;,, and which possess l 4 C atoms in the alkyl oralkenyl chain.

Suitable hetoryalkyl radicals Q are, for example, furfuryl-(furylmethyl)or thenyl-(thienylmethyl) radicals.

Examples of heterocyclic compounds which are formed by V and Vconjointly with the N atom of the amide group are: morpholine-,piperidine-, N-methylpiperazine, thiomorpholine and thiomorpholinedioxide.

Within the compass of the formula (I), dyestuffs to be regarded asparticularly preferred are those which correspond to the formulae R;(IIc) N l h (11d) wherein R R, and X have the abovementioned meaning andll l or, their functional derivatives, wherein A and R R have thealmvementioned meaning with compounds of the formula XCH -CN wherein Y Xhas the abovementioned meaning.

The condensation is carried out in the presence or absence of a solventor diluent, preferably with the addition of an alkaline catalyst, atelevated temperature, preferably in the range of (10 120C.

Suitable solvents or diluents are those which are inert under theconditions of the condensation and are able sufficiently to dissolve thereactants, and from which the reaction products separate out well. Forexample, methanol, ethanol, Z-methoxyethanol, isopropanol, dioxane,benzene, toluene, chlorobenzene, chloroform and pyridine are used.

As examples of alkaline catalysts, sodium hydroxide, potassiumcarbonate, sodium acetate and preferably secondary organic bases such asdiethylamine and especially pyrrolidine or piperidine should bementioned.

The reactants can be employed in molar ratio but an approximately 5percent excess ofthe cyanoacetic acid ester component (3) isadvantageous. It is also possible to choose a larger excess ofcyanoacetic acid ester without thereby adversely influencing the courseof the reaction.

Mixtures of aldehydes (Ill), such as are obtained during theirmanufacture, described later, are also very suitable as startingmaterials for the preparation, according to the invention, of the newdyestuffs (l).

Examples of suitable aldehydes of the formula (III) are:

JIN

m (l ll5 \J inc :Cll- CllO ll IIzO =CIICHO CH3 o II C =C--CIIO Li 1130-=CHCHO Examples of suitable cyanoacetic acid derivatives of the formulaIV are malodinitrile, cyanoacetic acid methyl ester, cyanoacetic acidethyl ester, cyanoacetic acid isobutyl ester, cyanoacetic acid3-meth0xybutyl ester, cyanoacetic acid isoamyl ester, cyanoacetic acidcyclohexyl ester, cyanoacetic acid p-methylcyclohexyl ester, cyanoaceticacid tetrahydrofurfuryl ester, cyanoacetic acid methyl ester,cyanoacetic acid dichloroisopropy] ester, cyanoacetic acid benzyl ester,cyanoacetic acid Z-chlorobenzyl ester, cyanoacetic acid 4- chlorobenzylester, cyanoacetic acid 3,4- dichlorobenzyl ester, cyanoacetic acid2,4,6- trichlorobenzyl ester, cyanoacetic acid 4-nitro benzyl ester,cyanoacetic acid metHylbenzyFes tfl cyanoacetic acid ester, acidB-phenylethyl ester, cyanoacetic acid ,B-hydroxy-B-phenylethyl ester,cyanoacetic acid y-phenylpropyl ester, cyanoacetic acid y-phenylallylester, cyanoacetic acid phenoxyethyl ester, cyanoacetic acidN-methylarnide, cyanoacetic acid N-ethylamide, cyanoacetic acidN-butylamide, cyanoacetamide, cyanoacetic acid N-methylanilide,cyanoacetic acid N-ethylanilide. cyanoacetic acid B-hydroxyethylamide,cyanoacetic acid methoxypropylamide, cyanoacetic acid fi-methoxyethylester, cyanoacetic acid B-chloroethyl ester, cyanoacetic acidB-cyanoethyl ester, cyanoacetic acid fi-hydroxyethyl ester, cyanoaceticacid n-propyl ester, cyanoacetic acid isopropyl ester, cyanoacetic acidallyl ester, cyanoacetic acid n-butyl ester, cyanoacetic acidp-methyoxybenzyl ester or mixtures of these cyanoacetic acidderivatives.

The new azolindoline dyestuffs of the formula (I) and (ll), especiallythe mixtures of these dyestuffs for ex ample mixtures of (Ila) and (lld)as well as (llb) and (lie) are outstandingly suitable for dyeing andprinting synthetic fibre materials and woven fabric materials ofaromatic polyesters and cellulose esters, but preferably of syntheticpolyamides and polyurethanes.

Using these dyestuffs, extraordinarily brilliant dyeings in yellowshades are produced on the fibres and woven fabrics mentioned, thedyeings being distinguished by particularly high colour strength, verygood build-up capacity and affinity and outstanding fastness properties,such as fastness to washing, to rubber, to

7 sublimation, to perspiration, to gas fume fading and to light.

The new dyestuffs of the formula (I) can be used for dyeing and printingin accordance with customary processes, for example in the form ofaqueous dispersions or printing pastes. The dye baths and printingpastes can contain the customary dyeing auxiliary additives such aslevelling agents, dispersiong agents and dyeing accelerators. Inaddition, the new dyestuffs can also be added to the spinningcompositions prior to spinning in the case of the manufacture ofsynthetic fibres.

Some types of the new dyestuffs can also be used advantageously fordyeing from organic solutions, for example from solutions in whichwater-immiscible solvents such as tetrachloroethylene,trichloroethylene, l,l ,Z-trichlorocthane or L1 ,l-trichloropropane areused.

A further subject of the present invention are indolines of the formulain which R and R independently of one another denote alkyl,

cycloalkyl or aralkyl or conjointly form a cycloalkyl ring,

R denotes hydrogen, alkyl, cycloalkyl, aryl or aralkyl, R denoteshydrogen, alkyl, nitrile, carbdmoyl, N-alkylcarbamoyl, alkoxycarbonyl oraralkoxycarbonyl,

R denotes hydrogen or an optionally modified aldehyde group and Arepresents the remaining members of a dibenzofurane radical which isoptionally substituted further,

as well as processes for their manufacture.

The radicals R R, and A have already been defined in more detail above.

By modified aldehyde groups R; there are especially to be understoodacetals, hydrates, oximes, ammoniates, aminals, bisulphite adducts andhydrazones.

Within the compass of the formula (1), compounds to be regarded aspreferred are those which correspond to the formulae (2a) (2d) Rt (\WA LL Il is \N/=CR4--R5 in which R, R have the abovementioned meaning andthe dibenzofurane radicals can carry further substituents, preferablychlorine and bromine atoms as well as methyl, methoxy and nitro groups.

Particularly preferred compounds (20) (2d) are those in which R, and Rdenote methyl,

R denotes methyl, ethyl, n-propyLi-propyl, n-butyl, B-chloroethyl,B-hydroxyethyl, ,B-cyanoethyl, B-methoxyethyl, ,B-bromoethyl,,B-acetoxyethyl or benzyl,

R, denotes hydrogen,

R denotes hydrogen or -CH0 and the dibenzofurane radicals do not carryany further substituents.

The new indolines of the formula l are obtained if indolenines of theformula -R2 A J CH in which R R and A have the abovementioned meaningare first reacted with N alkylating or N aralkylating agents R Y to givecompounds of the formula 'wherein A, R,, R and R have the abovementionedmeaning and Y represents the anionic radical originating from thealkylating or aralkylating agent these are converted in a manner whichis in itself known, under alkaline conditions, into the indolines of theformula In carrying out the quaternisation of the indolenines (3 anappropriate procedure is to react approximately equimolar amounts of thereactants with one another in a solvent which is inert under thereaction conditions, such as benzene, toluene, chlorobenzene,odichlorobenzene, chloroform, carbon tetrachloride, dioxane, ethylacetate or acetonitrile, at temperatures between 25 and l30C.

Suitable alkylating agents and aralkylating agents for convertingcompounds of the formula (3) into the formula (4) are, for example,alkyl halides such as methyl iodide, ethyl bromide, n-propyl bromide,i-propyl chloride, allyl bromide, N-butyl bromide, isoamyl chloride,sulphuric acid esters of lower alkanols such as dirnethyl sulphate ordiethyl sulphate, aromatic sulphonic acid esters such asp-toluenesulphonie acid methyl ester and ethyl ester.m-chlorobenzenesulphonic acid ethyl ester and substituted alkyl halidessuch as fi-chloropropionitrile, 4-hydroxybutyl bromide, phenylethylbromide, benzyl chloride. p-ehlorobenzyl chloride, p-methoxybenzylchloride. p-cyanobenzyl chloride, phenylacyl chloride, B-chloroaceticacid methyl ester, B-chloropropionic acid methyl ester, B-bromopropionicacid dimethylamide as well as acrylonitrile, ethylene oxide and others.

Dimethyl sulphate and diethyl sulphate are particularly preferred. Theliberation of the indolinemethylene bases of the formula (5) from thecorresponding salts of the formula (4) is achieved in a manner which isin itself known by dissolving the salts of the formula (4 for example inwater, and precipitating the methylene base by adding aqueous alkalisuch as sodium hydroxide solution or potassium hydroxide solution.

The methyleneindolines of the formula (5) can be converted in accordancewith formylation methods which are in themselves known into theindoline-waldehydes according to the invention, of the formula (I),wherein R CHO. This reaction can be carried out particularly simply andsmoothly if the formylation is carried out in accordance with theVilsmeier method. Suitable Vilsmeier formylation mixtures are obtained,for example, if phosphorus oxychloride, phosgene or thionyl chloride arereacted with tertiary formamides such as dimethylformamide orN-formyl-N- methylaniline; a mixture of equimolar amounts of phosphorusoxychloride and dimethylformamide is preferred. As solvents and diluentsit is possible to use, for example, excess dimethylformamide oracetonitrile. The reaction temperatures can be varied over a substantialrange without significantly changing the result. The reaction isadvantageously carried out at between 30 and 85C and preferably at 3560C.

The conversion of the free aldehyde group R into a functional derivativethereof can also be carried out in accordance with methods which are inthemselves known (compare, for example, Houben-Weyl; Volume Vll/l (4thedition) page 413488).

The introduction of the substituent R, can be effected in a manner whichis in itself known by treating the indoline compounds (5) with customaryC alkylating agents such as, for example, cyanogen bromide,isocyaiiatcs. chlorolormic acid esters, acrylonitrile, acrylic acidesters or acrylic acid amides.

The indolenines (3) which are required as a starting material for themanufacture of the new indolines (l) and which have hitherto not beendescribed are obtain- 10 able in .accordance'with various methods. Oneof these processes is characterised in that dibenzofuranehydrazines ofthe formula in which the benzene nuclei can carry further substituents,are reacted with ketones of the formula R1 ll ino-o-o in which R, and Rhave the abovementioned meaning in the presence of agents which splitoff water, such as zinc chloride, in a manner which is in itsellknown(lndole synthesis according to E. Fischer).

The hydrazines of the formula (6) are in part new and are obtainable,for example, by reduction of corresponding diazonium compounds.

A further process for the manufacture of the indolen- R and R have theabovementioned meaning and the benzene rings can carry furthersubstituents, in a manner which is in itself known (compare, forexample, Elderfield; (Heterocyclic Compounds, Vol. 2, page 124) withformation of the dibenzofurane ring system.

in both the methods mentioned for the preparation of the indolenines (3)isomer mixtures of these compounds are obtained, which can be separatedin accordance with customary processes (for example by fractionalrecrystallisation). In general it is however advisable to dispense withthese separation operations since the mixtures of indolenines (3) whicharise during their preparation, or the mixtures of indolines (1)prepared therefrom, are outstandingly suitable for the synthesis ofdyestuff mixtures which have the advantage of better affinity over thecorresponding pure dyestuffs.

EXAMPLE 1 are heated to the boil with 11.4 g of cyanoacetic acid ethylester in 65 ml of ethanol, 0.5 ml of piperidine is added and the wholeis kept at 80 for 3 hours. The mixture is cooled and the dyestuffmixture which has crystallised out is filtered off, washed with alcoholand dried. The interpretation of the NMR spectrum of this mixture showsa 57 percent content of the angularly arranged component (acharacteristic doublet at 6.87 ppm (for C and a superposed doublet atapprox. 7.85 ppm (for C,), with a coupling constant of 8.3 Hz) and 43percent of the linearly arranged component (two characteristic singletsat 7.73 ppm and 6.98 ppm, which are attributable to the two protons on Cand The aldehyde mixture used as the starting material was manufacturedas follows: 183 g of 3- aminodiobenzofurane are diazotised and thenreduced in the customary manner to the corresponding hydrazine. lfthisis reacted, in a known manner (G. Plancher, B. 31, page 1496) with 95 gof methyl isopropyl ketone to give the trimethylindolenine, 190 g of ayellow oil are obtained which is not purified further'but taken upimmediately in 300 ml of chlorobenzene, stirred with 562 ml of 50percent strength sodium hydroxide solution at room temperature undernitrogen and then treated dropwise with 200 g of dimethyl sulphate overthe course of 4 hours with vigorous stirring at The mixture is stirredfora further 2 hours, 1,500 ml of water are added, the whole is heatedto 90 and the organic phase is separated off and washed with water. Thetrimethyl-Z-methylene-indoline mixture thus obtained is then freed ofthe chlorobenzene under a waterpump vacuum.

Yield: 193 g of a yellow oil which crystallises slowly.

129 g of this mixture, the components of which possess the formulae areslowly added, at to a mixture of 94.6 g of phosphorus oxychloride and 49g of dimethylformamide. The resulting suspension is mixed for 8 hours atand is then stirred into a mixture of 34.3 g of 45 percent strengthsodium hydroxide solution and 1 kg of ice.

The mixture is stirred for a further 4 hours and the resultingcrystalline aldehyde mixture is filtered off. Yield: 125.6 g.

The components of this mixture have the formulae:

EXAMPLE 2 20 parts by weight of the dyestuff mixture obtained accordingto Example 1 arekneaded with parts by weight of the condensation productof formaldehyde and naphthalcnesulphonic acid and with a little wateruntil the dyestul'f is in a finely divided form. The paste is dried invacuo. I

A yarn of polymeric e-caprolactam is introduced at 50 into a dye bathwhich per litre contains 0.66 g of the dyestuffdispersion manufacturedin the manner described above and 0.5 g of a condensation product offormaldehyde and naphthalcnesulphonic acid. The liquor ratio is l 35.The bath is warmed to over the course of half an hour and dyeing iscarried out at this temperature for one hour. Thereafter the yarn isrinsed and dried. A very strong greenish-tinged yellow colourationof'very good brilliance and very good fastness properties is obtained.

EXAMPLE 3 If the procedure of Example 1 is followed and instead ofcyanoacetic acid ethyl ester a sufficient amount of cyanoacetic acidbenzyl ester is employed, a mixture of the dyestuffs The mixture dyespolyamide fabric in a strongly greenish-tinged yellow of highbrilliance, very good fastness to light and outstanding wet fastnessproperties. The following dye-stuff mixtures are obtained analogouslyusing the corresponding starting materials:

3.2 g of the aldehyde of the formula are stirred with 1.3 g ofcyanoacetic acid ethyl ester in 15 ml of ethanol in the presence of 0.1g of piperidine for 3 hours at the boil.

On cooling, 2.5 g of the dyestuff of the formula -OCH1 11 C N--CHa (3NJ=CH-CH=C/ 1130 COOCZHE synthetic fibres in a yellow having goodfastness properties are obtained: 2-bromo-3-aminodibenzofurane;3-amino-4-methoxydibenzofurane and 2,7-dimethyl-3- aminodibenzofurane.

EXAMPLE 49 If in Example 1 2-aminodibenzofurane is employed instead of3-aminodibenzofurane and in other respects the instructions of Example 1are followed a ,dyestuff mixture is obtained which according to the NMRspectrum consists to the extent of 74% of the angular structure and tothe extent of 26 percent of the linear component The dyestuffmixturcdyes polyamide fabric in a hrillant greenish-tinged yellow.

EXAMPLE so A woven fabric of polyethylene terephthalate is introduced,using a liquor ratio of l :40. into a dye bath at 50 which contains 0.5g/l of the finely divided dyestuff from Example 6 and l g/l of aconventional anionic dispersing agent, g/l of cresotic acid methyl esterand 1 g/l of NaH PO and is adjusted to pH 4.5 5 acetic acid. Thetemperature is raised to 80 85 over the course of minutes and themixture is left at this temperature for 20 minutes. Thereafter theliquor is slowly brought to the boil and is then left at the boil for 1hour. After rinsing and drying, a strongly greenishtinged yellow dyeingof high clarity and very good fastness to light is obtained.

Similarly good effects are achieved with the remaining dyestuffsdescribed above.

EXAMPLE 5i A knitted fabric of polyhexamethylenediamine adi patefilaments is impregnated at room temperature with a solution whichcontains 6 parts of dyestuff from Example 43 and 7 parts of nonylphenolheptaglycol ether in 989 parts of tetrachloroethylene. Aftersuction-draining to give a weight increase of 60 percent, the knittedfabric is dried for some minutes at 80. Thereafter the dyestuff is fixedby heating the knitted fabric to 192 for 45 seconds. The material isthen briefly washed with cold tetrachloroethylene. After drying, a veryclear greenish-tinged yellow dyeing is obtained.

Similarly good effects are achieved with the remaining dyestuffsdescribed above.

I claim:

1. lndoline dyestuff of the formula in which R. and R independently ofeach other, are methyl, ethyl, cyclohexyl, phenylalkyl of 1-4 carbonatoms in the alkyl portion, or phenylalkyl of 1-4 carbon atoms in thealkyl portion wherein the phenyl portion is substituted by chloro,C,-C,-alkyl or C -C alkoxy;

R and R when joined together are cyclopentyl or cyclohexyl;

R is hydrogen, C -C -alkyl, C -C -alkenyl, C,-C

hydroxyalkyl, C -C -hydroxyalkenyl, C -C chloroalkyl, C C-chloroalkenyl, C -C bromoalkyl, C,-C -bromoalkenyl, C -C cyanoalkyl, C-C -cyanoalkenyl, C -C alkoxy, -alkylosubstituted by C -C,-alkoxy, l-C-alkenyl substituted by C,-C,-alkoxy, C,-C,;-alkylosubstituted by CONH-C -C -alkenyl substituted by CONH C -C,,-alkyl substituted by C -Calkoxycarbonyl, C C -alkenyl substituted by C -C alkoxycarbonyl, C,-C,;-alkenyi substituted by C -C alkoxycarbonyl, -alkyl substituted byC -C,,-alkylcarbonyloxy, -alkenyl substituted by C C,- alkylcarbonyloxy,cyclohexyl, naphthyl, phenyl, chlorophenyl, bromophenyl, fluorophenyl, C-C alkylphenyl, C,-C,-alkoxyphenyl, phenylalkyl of 1-4 carbon atoms inthe alkyl portion, or phenylalkyl of 1-4 carbon atoms in the alkylportion wherein the phenyl portion is substituted by chloro, -C -alkyl,or C -C alkoxy,

LII

LII

alkoxy-carbonyl, pheiiyl-(C -Q-alkoxy) carbonyl.

substituted C,-C -alkyl or substituted C -C -alkenyl wherein thesubstituent insaid alkyl or in said alkenyl is chloro, bromo, cyano, C-C alkoxy, CONH C,-C,-alkoxycarbonyl, or C,-C,-alkylcarbonyloxy,

A has the formula 1; i d e or any of said four formulas substituted bychloro,

bromo, fluoro, C -C -alkyl, benzyl, C,-C -alkoxy, nitro, hydroxyl,cyano, CF C -C -alkylcarbonyl, C -C,-alkoxycarbonyl, carbamoyl, N-(C-C,-alkyl) carhamoyl, C ,-C,-alkylcarbonylamino, benzoylamino,toloylamino, sulphamoyl, N-(C -Q- alkyl) sulphamoyl, N,N-di(C -C,-alkyl)sulphamoyl, N,N-di(C,-C,-alkyl) sulphamoyl, C -C alkylsulphonyl,phenylsulphonyl, tolysulphonyl, phenoxy, tolyloxy, or benzyloxy;

and additionally, ring B may be substituted by a fused benzene ring; and

X is cyano, -CO Q, or -CONV,V where Q is C -C V and V independently ofeach other. are hydrogen, C -C -alkyl, C -C -alkenyl. C C hydroxyalkyl,C -c -hydroxyalkenyl, C -C -alkyl substituted by C -C,-alkoxy, C -C-alkenyl substituted by C -Q-alkoxy, phenoxy-C -C -alkyl, phenoxy-C -C-alkenyl, cyano-C -C -alkyl, cyano- C -C -alkenyl, cyclohexyl,methylcyclohexyl, cyclopentyl, phenyl-C -C alkyl, phenyl-C C alkenyl,substituted phenyl-C -C,-alkyl, or substituted phenyl-C ,-C,-alkenylwherein said substituted phenyl portions are substituted on the phenylring by nitro, chloro, bromo, fluoro, methoxy or methyl; and

V, and V when joined together with the N-atom, are

morpholino, piperidino, N-methylpiperazino, thiomorpholino, orthiomorpholino dioxide.

2. lndoline dyestuff ol claim 1 of the formula (Illa or is substitutedby chloro, bromo, nitro, or methyl.

3. lndoline dyestuff of the formula R R R R and X have the same meaningsas in claim 1 and the dibenzofurene radical is unsubstituted orsubstituted by chloro, bromo, nitro, or methyl.

4. lndoline dyestuff of the formula in which R,, R R R and X have thesame meanings as in claim 1 and the dibenzofurene radical isunsubstituted or substituted by chloro, bromo, nitro, or methyl. 5.lndoline dyestuff of the formula in which R,, R R R and X have the samemeanings as in claim 1 and the dibenzofurene radical is unsubstituted orsubstituted by chloro, bromo, nitro. or methyl. 6. lndoline dyestuff ofthe formula in which R,, R R R and X have the same meanings as in claim1 and the dibenzofurene radical is unsubstituted or substituted bychloro, bromo, nitro, or methyl.

7. lndoline dyestuff of the formula in which R, and R denote methyl,

R denotes methyl, ethyl, n-propyl, i-propyl, n-butyl, B-chloroethyl,B-hydroxyethyl, B-cyanoethyl, B-methoxy-ethyl, B-bromoethyl,B-acetoxyethyl or benzyl,

R, denotes hydrogen or cyano and X represents cyano, C -C,-alloxycarbonyl, methoxy (C -C alkoxy) carbonyl, cyclohexoxycarbonyl,methylcyclohexoxycarbonyl, cyclopentoxycarbonyl, methyl phenyl (C -Calkoxy) carbonyl, nitro =phenyl(C -C -alkoxy) carbonyl, methoxy phenyl(C -C,,-alkoxy) carbonyl, chloro phenyl (C -C alkoxy) carbonyl, orphenoxy (C -C alkoxy) carbonyl.

8. lndoline dyestuff of the formula Ri v/ wm -Rz 0N 6O o-orr=o N l l lR'4 x 0 R; -R2

/CN 5 In which I N L R R, and X have ,the meaning mentioned in claim 9.lndoline dyestuff of the formula 10. lndoline dyestuff of the formula ONC C-OH: \N/\C CO:O l I l B3 A XI R3 R4, X!

in which in which R R and X have the meaning mentioned in claim R, R andX have the meaning mentioned in claim 7 =l l

1. INDOLINE DYESTUFF OF THE FORMULA
 2. Indoline dyestuff of claim 1 ofthe formula
 3. Indoline dyestuff of the formula
 4. Indoline dyestuff ofthe formula
 5. Indoline dyestuff of the formula
 6. Indoline dyestuff ofthe formula
 7. Indoline dyestuff of the formula
 8. Indoline dyestuff ofthe formula
 9. InDoline dyestuff of the formula
 10. Indoline dyestuff ofthe formula